1-acylamino-4-[(nudialkylamino)-sulfonamido-renzoylamino]-anthraquinones



Patented May 2, lfisfi urrro STATES Fat ENE QFHQE;

1 -ACYLAMINO-4 (N DKALKYLAMENU) SULFONAMIDO EENZGYLAMINO] -AN- THRAQUINONES Switzerland .No Drawing. Application November 17, 1947, Se-

rial No. 786,546. In Switzerland November 18,

7 Claims. (Cl. 260-272) The present inventionis concerned with vat dyestuifs of the anthraquinone series. More particularly the invention refers to lz l-di-acylaminoanthraquinones containing acylamino radcais in the 1- and l-positions which are different from one another.

It is an object of the presentinvention to provide new and valuable vat dyestuffs of the said series which constitute an enrichment of the art for different reasons such as enhanced purity of shade, fastness to diverse wet treatments, or other valuable properties. More particularly it is an object of the present invention to provide new dyestuffs of the above series which are superior to previous ones for the reason that they cause less damage to the dyed fibers on exposure to light.

It is well known inthe artthat all vat dyestufis as far as present knowledgegoes are not absolutely fast to light. Therefore, alldyeings on sufficiently long exposure to light show well visible marks of deterioration in that the dyeing changes its shade or hue, crfades away,: or shows both deficiencies. Apart fromthis there is mostly some change in the fiber too, i. e.the-cotton fibers or rayon fibers, etc., themselves, whether dyed on not, undergo-some deterioration on prolonged exposure to light, or asthe case maybe, in combination with exposure to rain, moisture, etc. It has long been ascertained that under such exposure cotton or similar fibers dyed with certain dyestuffs are more quickly damaged, or to a greater extent, than those dyed with other dyestuffs. Unfortunately, in the series of l:4-diacylalninoanthraquinones there are many dyestuffs, including somewhich contain sulfamido benzoylainino groups, which while otherwise possessing excellent properties, have the disadvantage of causing enhanceddeterioration of the fiber dyed therewith. larly, it is an object of the present invention to provide new dyestuffs of the group referred to, which contain sulfamido benzoylaznino groups, but are distinctly less liable to cause the undesirable fiber deterioration. in part be obvious and in part apnear as the specification proceeds.

According to the present invention l-acy1- aminol[ (N di-allryl sulfonainido ,benzoylamino]-anthrao,uinones are made by treating a 1-amino-4-acylaminoanthraquinone with an acylating agent and so choosing the l-aminolacylamino-anthraquinone and the acylatlng agent that the product of the acylationcontalns in one amino group thevresidue of aheterocyclic More particu- Other ob ects will 22 carboxylic acid and in the other amino group the residue of an N-dialkylsulfonamidobenzoic acid.

The components may be so chosen in accordance with the present invention that, for example a l-arnino-l- (N-dialkyl) sulfonamidobenzoylaminol -anthraquinone is treated with an acylating agent which is capable of introducing the residue of a heterocyclic carboxylic acid. The starting material used in this form of the inventicn may contain in the l-position, for example, a para-dimethyl-sulfonamidobenzoylamino group or a para diethylsulfonamidobenzoylamino group. The dialkyl-sulfonarnido group may also be so constituted that the two alkyl groups together form a ring, as in the case of the parasulfopiperidido-benzoyiamino group or para-sulfomor'oholido-benzoylamino group.

As examples of heterocyclic carboxylic acids which may be reacted as such or preferably in the form of their reactive functional derivatives, for example, their acid chlorides, with the amino group in the 1-position of the anthraquinone residue, there may be mentioned a very wide variety of pyridine carboxylic acids, especially pyridine- 3-carhoxylic acid, and also quinoline carboxylic acids, thiophene carboxylic acids and furane carboxylic acids.

The reaction of the 1-amino-4-l(N-dialkyl)- sulfonamido-benzoylaminol-anthraquinone with the heterocyclic carboxylic acid or functional derivative thereof may bencarried out that is to say, advantageously in an inert, preferably high boiling, solvent or diluent such as chlorobenzene, dior trichlorobenzene, chloronaphthalene, naphthalene or nitrobenzene.

Similar or identical dyestuffs can be obtained in accordance with this invention by treating a l-acylarninoiaminoanthraquinone, which contains as the acyl residue the residue of a heterocyclic carboxylic acid, with a benzoylating agent which contains a dialkyl-sulfonamido group in the benzoyl residue. In this form of the invention the heterocyclic acyl residue may be that of one of the heterocyclic carboxylic acids mentioned above, and there may be chosen with advantage as a benzoylating agent a functional derivative of a dialkylsulfonamidobenzoic acid, for example, i-i-dimethylor l-Ndiethyl-sulfonamidobenzoic acid.

In both forms of the invention described above a l-aminol-acylamino-anthraquinone is treated with an acylating agent and the starting materials are so chosen that one of the acyl residues corresponds to the residue of a heterocyclic carboxylic acid and the other acyl residue to the residue of a dialkyl-sulfonamidobenzoic acid. The appropriate 1-amino-l-acylamino-anthraquinone may be prepared in a simple manner by treating a 1-nitro-4-aminoanthraquinone with the appropriate acylating agent, and then reducing the nitro group. The above mentioned 1-amino-4-acylamino-anthraquinones may contain further substituents, especially a halogen atom of the 6- or Z-position.

The products of the present invention are valuable vat dyestuffs. They can be used in known manner for dyeing or printing a very wide variety of fibers of animal, and especially vegetable character, for example, wool, silk, and especially cotton, linen, artificial silk or staple fibers of regenerated cellulose, and polyvinyl fibers. There are obtained dyeings which are in part pure and fast, and of which in some cases the low tendency to injury of the fibers by exposure to light and weathering may be of linportance.

The following examples illustrate the invention, the parts being by weight:

Example 1 2.5 parts of pyridine-fl-carboxylic aci 4.8 parts of nitrobenzene and 3.0 parts of thionyl chloride are stirred at 120-130 C. for 1 hours, then 9.0 parts of l-aminol-[Bar-(N-dimethyl)- sulfonamido-benzoylamino]-anthraquinone are added, and the whole is stirred at that temperature for a further 2 hours. After cooling, the resulting dyestuff of the formula is separated by filtration, washed with alcohol, and dried. It forms red crystals, which dissolve in concentrated sulfuric acid with an orange coloration, and dye cotton from a grey-blue vat pink tints.

The dyestuff is also suitable for printing by the usual potash printing process.

Example 2 17.5 parts of quinoline-S-carboxylic acid are suspended in 400 parts of dry nitrobenzene, and, after the addition of 15 parts of thionyl chloride and a small quantity of pyridine, the whole is stirred at 110-120 C. for 1 hours. The whole is then mixed with 45 parts of l-(para-sulfodimethylamido benzoylamino) i-aminoanthrawhich precipitates upon cooling in the form of a crystalline red powder is washed well with boiling alcohol and dried. It dissolves in concentrated sulfuric acid with a red coloration and dyes cotton from a blue-green vat fast powerful pink tints.

Example 3 18 parts of quinoline-B-carboxylic acid are suspended in 600 parts of dry nitrobenzene, and, after the addition of 17 parts of thionyl chloride and a small quantity of pyridine, the whole is stirred at -120" C. for /2 hours. The whole is then mixed with 48 parts of 1-amino-i-(parasulfodimethylamido benzoylainino) 7-chloranthraquinone and further stirred for 3 hours at -130 C. The dyestuif which precipitates upon cooling in the form of a crystalline red powder is thoroughly washed with boiling alcohol and dried. It dissolves in concentrated sulfuric acid with a red coloration and dyes Cotton from a blue-green vat fast pink tints. It is well suited for dyeing at a medium temperature of about 40-56 C.

The aforesaid l-aminol-(para-sulfodimethylamido-benzoylamino) 7 chloranthraquinone is obtained in the following manner:

120 parts of benzene-l-carboxylic aoid--(N- dimethyl) -sulionamide are suspended in 800 parts of dry nitrobenzene, and, after the addition of '78 parts of thionyl chloride, the whole is stirred for 2 hours at 120 C. 150 parts of 1-amino-4- nitro-6-chloranthraquinone are then added, and the whole is stirred for a further 3 hours at 120- C. Upon cooling, the acylated aminoanthraquinone crystallises in the form of small yellow crystals, which are separated by filtering with suction and washed thoroughly with boiling alcohol. 175 parts of the latter product are stirred with 300 parts of phenyl hydrazine in 1300 parts of ortho-dichlorobenzene for 1 hour at 0. Upon cooling, 1-amin0-4-(para-sulfodimethylamido benzoylamino) 7 chloranthraquinone precipitates in the form of small violet crystals.

Example 4 27 parts of benzoic acid-i-sulfopiperidide are suspended in 250 parts of dry nitrobenzene, and, after the addition of 15 parts of thionyl chloride and a very small quantity of pyridine, the whole is stirred for 1 /2 hours at 115-120 C. The whole is then mixed with 36.5 parts of l-furfuroylamino- 4 amino 6 chloranthraquinone and further stirred for 2 hours. The dyestuif of the formula which precipitates upon cooling in the form of red crystals is separated by filtering with suction, thoroughly washed with boiling alcohol, and dried. It dissolves in concentrated sulfuric acid with a grey-violet coloration and dyes cotton from a blue-green vat very pure fast pink tints.

A similar dyestulf is obtained by using benzoic acid-4-sulfomorpholide, instead of benzoic acide-sulfopiperidide.

The foregoing 1-furfuroylamino i-amino-S- chloranthraquinone is obtained in the following manner:

33.6 parts of furane-a-carboxylic acid are suspended in 400 parts of dry nitrobenzene, and after the additiomof r4531arts of thionylichloride and a very small quantitynf pyridine, the whole is stirred for 1 /2 hours at 70 80 C; The whole is then mixed with 90 parts of 1-amino-4-nitro-6- chloranthraquinone andwstirred for; a further 2 hours at 120-430 C. Upon cooling theracylated aminoanthraquinone precipitates, in the form of small yellowneedles which are repeatedly Washed with boiling alcohol. ,The nitro group is reduced violet crystals.

Example 6 18.4 parts of benzene-l-carboxylic acid-4-(N- dimethyll-sulfonamide are suspended in 550 parts of dry nitrobenzene, and, after the addition of 12 parts of thionyl chloride and a small quantity ofi pyridine, the. whole is: stirred for l hours at 100410 0.. 34parts, of l-,-(quinoline -6.-carin theimanner described in Examnle 3' 1..fur boyleamino).-4-amino-6echloranthraquinone are. furoylamino 4 e amino, 6 -chlorahthraquingne then added, and the whole is stirred for a further forms small vi01et-crstals when recrystallized 2 hours at h whole is finally heatfr m orthmdichlombenzene: ed up to 175 C. in the course of hour and then allowed to cool. Theidyestufi, which precipitates Example 5 in the form of a fine crystalline red powder, is 27 parts of benzoic acid para-sulfomorpholide by filtering with suction, thoroughly are suspended in 250 parts of drynitrobenzene, Washed; Wlth boilmg alcohol a q It (115' and, after the addition of 15 parts of thionyl chlo- Solves P confleqntl'ated Sulfunc 361d Wlth F ride and a small quantity ,of pyridine, the whole is 9 i f f f from a green j blulsh stirredfor 1% hours at 110-120 0. The whole is 32 g gg ggg g g r .IIV g gg g figg Yi i il fig f i iifigg g sg ggit acid-{l-suliomorphol ide instead of benzene-l-carand further stirred for 2 hours at 120M30 c boxyhcapldii'mmmethyl)"silfonamme'. U d t f th f 1 l (qu1no11ne- G'- carboylamino 4- ammo- 6-, pon commg 8 yes 0 e :.ch1oranthraquinone can be obtained, for exam,-

ple, in the following manner: 0 NHCO parts of quinoline-S-carboxylic acid are H I stirred in 720 parts of dry nitrobenzene with 30 parts of thionyl chloride and-a small quantity of N 30 pyridine for 1 hours at ll0-120 C. The whole l is then mixed with parts of l-aminoi-nitro- I E 6-ch10ranthraquinone and stirred fora further NH-OO- -SOn I 0 zrhours at -1309-(3. After cooling, the nitro compound which precipitates in the form of yellow crystals, is thoroughly washed with boiling precipitates in :the form of a fine, crystalline red alcohol and dried. It may be reduced, for expowder, which is separated by filtering with sucample, by the method described in Example 3. tion, thoroughly washed with boiling alcohol. and The reduction product-forms violet crystals when dried. It dissolves in concentmtedsulfuric acid recrystalliaed from 0rtho-dichlorobenzene with a red coloration and dyes cotton from an 40. In simllalfmanner the dyestuffs in the followolive-green vat fast bluish pink tints. It is well mg table, which ave the general formula suited for dyeing at a medium temperature of 0 NH-residue of e t y c oxabout LO-50C. l 1 yhc acld By using benzoic acid-4-sulfopiperidide or benzene 1 carboxylic acid 4 (N dimethyl)- i sulfonamide, instead of benzoic acid--sulfo- :zgrfiphohde, there is obtained a veiy similar dye IlmLC g r%?$ The aforesaid 1-(pyridine-3 -carboylamino) can be obtained.-

H to c 1' arbo re id t i Sulf mid c o t id 5; f i e 1'0 yc l0 0 xy 1 8C Rglg one 8 gTOllP suljlfgll licljgeid the vat SOZEABCOttXJZ 11g Quinoline-ircarboxylic acid- 7-chloro-t i-snliomorpholido red blue-green... pink. Furane-2-carboxylic ZCidL'... 4-su1fodimethylamido brown-red... violet Do.

Do do.-. grey-violet" violgt-greenbluish-pink. Pyridine-Scarboxylicacid 4-sulfomorpholido; red b1:1 G- ViO18t. pink.

0 .e i-sulfopiperidido ..do do Do. Thiophene-zcarboxylic acid 4-sulfodimcthylamido brown-red... do Do.

4 amino 6 chloranthraquinone is obtained in the following manner:

3'7 parts of nicotinic acid are suspended in 600 parts of dry nitrobenzene, and after the addition of 44 parts of thionyl chloride and a very small quantity of pyridine, the whole is stirred at 120- C. 98 parts of 1-amin0-4-nitr0-6-chlor anthraquinone are then added, and the whole is stirred for a further 2 hours at the same temperature. The yellow powder precipitated upon cooling is separated by filtering with suction and thoroughly washed with boiling alcohol, and may be reduced, for example, in the manner described in Example 3. When recrystallized from ortho" What we claim is: 1. A vat dyestufi' of the general formula NH-C 0-3;

and thiophene-carboxylic acids, R2 stands for a 4. The vat dyestufi of the formula benzene radical carrying the -CO and o NH-oo X H S:-N/ 5 N groups in para position to one another, each X IE4; stands for an alkyl radical and at most one Y stands for a halogen atom, the remaining Y CH:

standing for hydrogen. 5. The vat dyestuif of the formula 2. A vat dyestuff of the general formula rgH- 0 0- 0 NHC O-R X 6. The vat dyestufl of the formula wherein COR1 stands for the radical of a O pyridine-carboxylic acid, R2 stands for a benzene radical carrying the CO and [i 0 II I X --SOaN groups in para-position to one another, each X The Vat dyestuff of the formula stands for an alkyl radical and at most one Y stands for a halogen atom, the remaining Y O standing for hydrogen. l 1

3. A vat dyestuff of the general formula O lTIH-C O-Ri ll H: 0 NH-COOSO2N Y GHa WALTER JENNY. NH. C() ,R .sQ, .N\ WALTER KERN.

X REFERENCES CITED wherein Stands for the radical f The following references are of record in the quinoline-carboxylic acid, R2 stands for a benzene file of 131115 p radical carrying the -CO and. 0 UNITED STATES PATENTS X 0 Number Name Date 2,043,985 Beard June 16, 1936 SO:N\ 2,079,940 Kunz et a1 May 11, 1937 X 2,190,751 Zerweck et a1 Feb. 20, 1940 2,356,061 Irving et a1 Aug. 15, 1944 groups in para-position to one another, each X 2,430,771 Kern Nov. 11, 1947 stands for an alkyl radical and at most one Y 2,439,626 Kern Apr. 13, 1948 stands for a halogen atom, the remaining Y standing for hydrogen.

Certificate of Correction Patent No. 2,506,023

May 2, 1950 WALTER JENNY ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 8, lines 7 to 1-0, inclusive, for that portion of the f0 rmula reading CH CH: eom read som \CHI OH and that the said Letters Patent should be read with this correction therein that the same rnay conform to the record of th e case in the Patent Office. Signed and sealed this 29th day of August, A. D. 1950.

THOMAS F. MURPH Y,

Assistant Commissioner of Patents. 

1. A VAT DYESTUFF OF THE GENERAL FORMULA 